Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE

Y02E60/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation

Y02E60/30—Hydrogen technology

Y02E60/32—Hydrogen storage

Y02E60/324—Reversible uptake of hydrogen by an appropriate medium

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

This invention provides an aligned single-layer carbon nanotube bulk structure, which comprises an assembly of a plurality of aligned single-layer carbon nanotubes and has a height of not less than 10 μm, and an aligned single-layer carbon nanotube bulk structure which comprises an assembly of a plurality of aligned single-layer carbon nanotubes and has been patterned in a predetermined form. This structure is produced by chemical vapor deposition (CVD) of carbon nanotubes in the presence of a metal catalyst in a reaction atmosphere with an oxidizing agent, preferably water, added thereto. An aligned single-layer carbon nanotube bulk structure, which has realized high purity and significantly large scaled length or height, its production process and apparatus, and its applied products are provided.

Description

Monolayer force one carbon nanotubes and aligned single-walled carbon nanotube 'bulk structure and method, apparatus and applications art their production

The invention of this application, a shall relates to a carbon nanotube (C NT) and aligned single-walled carbon nanotube Noruku structures and methods, devices and applications for their preparation, more particularly highly purified unprecedented high ratio surface area of, Rajisuke Lumpur reduction, carbon nanotubes and aligned single-walled carbon nanotubes "Parc structure to achieve a patterning of and methods for their preparation. Those about the device and application. BACKGROUND

The new electronic device materials, optical element materials, conductive materials, the carbon nanotubes development of functional materials as bio-related materials are expected (CNT), the yield, quality, use, productivity, production process, etc. study of has been vigorously pursued. One method of manufacturing a carbon nanotube, a chemical vapor deposition (CVD) method (hereinafter, referred to as CVD method) may, this method has attracted attention as being suitable for mass production. The C VD method is for the Toku徵 contacting with the catalyst metal fine particles of carbon compounds as a carbon source at a high temperature of about 5 0 0-1 0 0 0, catalyst type and placement, Ya kinds of carbon compounds is possible many variations by operating conditions, both single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (M WCNT) and is capable manufactured. Further, the catalyst with a child placed on the substrate, characteristics of a force one carbon nanotubes oriented vertically to the substrate surface can be grown; ^ is.

However, in the production of carbon nanotubes by conventional CVD methods, for incorporation catalyst or by-products that were generated carbon nanotubes, in order from the product obtain highly pure force one carbon nanotube, various chemical processing performed purification process was required. This purification process is a process complex and costly acid treatment such as a combination multiple had with requires considerable skill, causing the cost of the resulting product. Moreover, even with such a purification process, the purity of a limit to about 9 0~ 9 4m ass%, is to obtain a single-walled carbon nanotubes 9 8 mass% or more purity the difficult (Nanoletters 2, 385 (2002)) "Further purification, if chemical and physical properties of the carbon nanotube you change many, always been difficult to easily obtain carbon nanotubes of constant quality.

In the growth of carbon nanotubes by conventional CVD method, short active life of the metal catalysts, will be active in several tens of seconds is deteriorated, the growth rate of carbon Nanochi Yubu also there is a problem that not so large , which has been a cause that prevents mass production.

From such circumstances, it crushed immersion the board in a mixed aqueous solution of F e C 1 3 and hydroxyl § Min By catalyst preparation, and a method of controlling the growth of the iron catalyst activity and carbon nanotubes have been proposed Some (Hee Cheul Choi, et al, the field 0 LETTERS, Vol 3, No. 2, 157 -.. 161 (2003)).

However, despite such proposals, the for extension and growth rate of increasing size of the life of the catalytic activity is not still a satisfactory in practical use is in reality.

On the other hand, single-walled carbon nanotubes among carbon nanotubes, very good electrical properties (maximum current density very large), and thermal properties (thermal conductivity comparable to Diamon de), optical properties (optical communication emission at band wavelength), hydrogen storage capacity, nanoelectronic Depaisu Ya nano optical elements for such metal catalyst supporting ability, has attracted attention as a material for energy storage and the like. The single-walled carbon nanotubes these nanoelectronic devices, when chromatic criminal investigation utilized as materials such as nano-optical devices, energy storage, Shi name the Parc structure oriented single-walled carbon nanotube is in the form of a plurality of gathered assemblage , the bulk structure is electric and electronic, arbitrary desired to exhibit the functionality of the optical or the like. Further, it is desirable that these carbon nanotubes' Parc structure is desirably oriented in a particular direction, for example vertically aligned, and the length (height) is large scale. Previously as Parc structure multiplicity of vertically aligned single-walled force one carbon nanotube which has been reported to aggregate, its height is reported to have reached 4 m (C n Phys. Let t. Vol. 385 , p. 298 (2004)) 0

Further, a plurality of force one carbon nanotubes vertically aligned is a bulk structure, Bata-learning of are things, very suitable nanoelectronic devices as described above, the application to nano-optical element Ya Eneru ghee storage, etc. it is intended. However, albeit that achieved patterning of a multi-walled carbon Nanochi Yubu (Science 283, 412 (1999)), reported to have achieved the patterning of a single layer force one carbon nanotube it has not been such heretofore.

Single-walled carbon nanotubes compared to the multi-walled carbon nanotubes, superior-strength properties, flexural properties, flexural properties, higher light transmittance, larger specific surface area, more excellent electron emission characteristics, superior electrical conductivity, Further, with respect to multi-walled carbon nanotubes that metal, semiconductors and excellent characteristics such as metal both are present, if such a vertically aligned single-walled carbon nanotube Parc structures are created, nanoelectronic devices , during purification but application to nano-optical devices, energy storage, and the like are expected to large increase dramatically, except strong single-walled carbon nanotubes for Fandirusuwa one Ruska is very Kutsukki and immediately example impurities easily it would constitute a non-orderly-unoriented bulk structure, disordered, non-oriented path torque structure made once Rebuilding the body, for example, by the difficulty or the like to disperse the single-walled carbon nanotubes in the solution, it is extremely difficult, for reasons such as, but not at present such Parc structure is obtained is the current situation. Therefore, the invention of this application, provide the above-described from the background, high purity not found in conventional carbon nanotubes high specific surface area (especially oriented single-walled carbon nanotube Parc structure) and its manufacturing method and a device It is an object of the present invention to. The invention of this application, without the use of special organic such as hydroxyl § Min in the proposed method, by simple means, to extend the life of the metal catalyst, efficient carbon nanotube at high growth rate to achieve growth, and another object is to provide a carbon nanotube and its manufacturing method and a device excellent in mass productivity.

The invention of this application, high purity, has a high specific surface area, and the length is Inami height of rapid orientation achieved large scale monolayer carbon nanotubes Parc structure and its to provide a manufacturing method and a device that has a different problem.

Further, the invention of this application has been to provide a path evening aligned single-walled force one to achieve one training of Bon'nano tube Parc structure Contact Yopi its manufacturing method, apparatus and other problems.

The invention of this application, the high-purity carbon nanotube contact and the high purity of the high specific surface area, rapid La one Jisukeru aligned single-walled carbon nanotubes to achieve reduction of a high specific surface area a and a length or height Parc structure further has another object of application of the aligned single-walled carbon nanotube bulk structure which achieves the putter training of nanoelectronic devices, the nano-optical devices, energy storage, and the like. This application provides the following inventions as to solve the foregoing problems.

Opening single-walled carbon nanotube according to any one of [8] to [1] the specific surface area is equal to or less than 1600 m 2 / g or more 2500 m 2 / g (3).

Opening single-walled carbon nanotube according to the above [7] or [8], wherein the [9] the specific surface area is less than 1800 m 2 / g or more 2300 m 2 Zg.

[10] single-walled carbon nanotube according to any one of it is obtained by orienting the above [1], wherein the [9].

[11] single-walled carbon nanotube according to that they are vertically aligned on a substrate from above [1], wherein any one of [10].

[12] The carbon nanotubes in the presence of a metal catalyst in a method for chemical vapor deposition (CVD), the production method of carbon nano tubes, which comprises adding an oxidizing agent to the reaction atmosphere.

[13] method for producing a carbon nanotube according to the above [12] to Toku徵 the oxidizing agent is water vapor.

[14] force one carbon nanotube production method described in [13], wherein the addition of 10 ppm or more 10000 p pm or less of water vapor.

Method for producing a carbon nanotube according to [15] above the addition of steam at a temperature below 600 or 1000 to FEATURE: [13] or [14].

Method for producing a carbon nanotube according to any one of [16] [15] from the [1 2], wherein the carbon nanotube is a single layer obtained.

[17] the production method of the force over Pont nanotube according to any one of the catalysts to the growing carbon nanotubes oriented vertically to the substrate surface disposed on a substrate from the [12] to Toku徵 [16].

Method for producing a carbon nanotube according to any one of the above SL to [18] in length and wherein the obtaining the carbon nanotubes over 10 tm [12] to [17].

Manufacturing method of a carbon nanotube according to any one of [19] length is equal to or get the following carbon nanotube 10 / m or more 10 cm [12] to [18].

[20] After growing the force one carbon nanotube, a carbon nanotube according to any one that can be separated from the catalyst or the substrate without exposing the solution and the solvent from the [12] to Toku徵 [1 9] the method of production.

[21] method for producing a carbon nanotube according to any of that purity obtained carbon nanotube is 98ma ss% or more from the [12] to FEATURE: [20].

[22] method for producing a carbon nanotube according to any of that purity obtained carbon nanotube is 99ma ss% or more from the [12] to FEATURE: (21).

[23] purity 99. 9m carbon nanotube manufacturing method according to any of as the from [12] [22], wherein the obtaining the carbon nanotube is s% or more.

[24] specific surface area of 600 meters 2 / g or more 1300 m 2 / g or less unopened monolayer force - from the [12] to Toku徵to obtain a carbon nanotube of the carbon nanotube of any crab according [23] Production method.

[25] specific surface area of 800 m 2 / g that over 1200 m 2 / g to obtain a unopened monolayer force one carbon nanotube or less from the [12] to Toku徵of carbon nanotubes of any crab according [24] Production method.

[26] specific surface area of 1600 m 2 Zg least 2500 m 2 / g or less is opening monolayer force - how carbon nanotubes in manufacturing any crab description to obtain a carbon nanotube from the [12] to Toku徵[23] .

[27] The specific surface area is from the [12], wherein the obtaining the opening monolayer force one carbon nanotube is not more than 1800 m 2 / g or more 2300 m 2 Zg [23], carbon according to any one of [26] method of manufacturing the nanotubes.

[28] a plurality of aligned single-walled carbon nanotubes, aligned single-walled carbon nanotube Parc structure to Toku徵 the height is more than 10 m.

[29] aligned single-walled carbon nanotube Parc structure described in [28], wherein the height is less than 10 m or more 10 cm.

[31] aligned single-walled carbon nanotube Parc structure according to any one of the purity of 99ma ss% or more from the [28] to Toku徵 [3 0].

[32] aligned single-walled carbon nanotube Parc structure according to any one of [28] or et al purity, characterized in that at 99. 8ma ss% or more [31].

Aligned single-walled carbon nanotube 'bulk structure according to any one of [33] above [28] or al a specific surface area, characterized in that it is 600 meters 2 / g or more [32].

[34) aligned single-walled carbon nanotube 'bulk structure according to any one of, wherein the specific surface area of 800 m 2 / g or more 250 Om 2 / ^ or less from the [28] [32].

Aligned single-walled force one Bon'nanochu over blanking Parc structure according to any one of [35] that the specific surface area is less than 1000 m 2 / g or more 2300 m 2 / g from the [28] to Toku徵[34].

[36] specific surface area of 600 meters 2 / g or more 1300 m 2 Zg is less unopened monolayer force - aligned single-walled carbon nanotube Parc structure according to any one of consisting of carbon nanotubes from the above-mentioned [28] [32] .

[37] The specific surface area is from the [28], wherein the formed of unopened monolayer force one carbon nanotube is not more than 800 m 2 Zg least 1200 m 2 / g [32], according to any one of [36] single-walled carbon nanotube Parc structure.

[38] The specific surface area is aligned single-walled according to any Re [32] Noise from the [28], wherein the formed of the opening monolayer force one carbon nanotube is not more than 1600 m 2 Zg least 2500 m 2 / g carbon nanotube bulk structure.

[3 9] that the specific surface area is from 1 8 0 0 m 2 Zg least 2 3 0 0 m 2 / g in which the opening monolayer force one carbon nanotube or less from the [2 8] to Toku徵[3 2] , aligned single-walled carbon nanotube Parc structure according to any one of [3 8].

[4 1] size of the alignment direction perpendicular to the direction of anisotropy in it, one for the value of the lesser value larger: in [4 0] to Toku徵 that is three or more single-walled carbon nanotube bulk structure according.

[4 2] The size of the alignment direction perpendicular to the direction of anisotropy in it, one for the value of the lesser value larger: the [4 0] to Toku徵 to 5 or more or [4 1] SWNTs Parc structure according to.

[4 3] The size of the alignment direction perpendicular to the direction of anisotropy in it, one for the value of the lesser value larger: the [4 0] to Toku徵 to be 1 0 or more monolayer force one carbon nanotube 'bulk structure according to any one of [4 2].

[4 4] aligned single-walled carbon Nanochi Yubu Parc structure according to any one that he or she can get not exposed to the solvent and solvent from the [2 8] to FEATURE: of [4 3] body.

[4 5] aligned single-walled carbon nanotube bulk structure according to any one of the shape of the Parc structure is patterned into a predetermined shape from above [2 8] to Toku徵 [4 4] body.

[4 6] aligned single-walled carbon nanotube Parc structure according to any one of the vertically aligned on a substrate from the [2 8], wherein the [4 5].

[4 7] aligned single-walled carbon nanotube Parc structure according to any one of the bulk structure is a thin film from the above [2 8] to Toku徵 [4 6].

. [4 8] The metal catalyst is patterned on a substrate and a plurality of single-walled carbon nanotubes by chemical vapor deposition (C VD) ​​to orient in a predetermined direction against the substrate surface in the presence of the metal catalyst a method according to Parc structure, manufacturing method of the aligned single-walled carbon nanotube Parc structure characterized by adding an oxidizing agent to the reaction atmosphere.

[4 9] the production method of the aligned single-walled carbon nanotube Parc structure according to [4 8] to Toku徵 the oxidizing agent is water vapor.

[5 2] the production method of height 1 0 zm to obtain a more Parc structures and Toku徵 the aligned single-walled carbon nanotube Parc structure according to any one of [4 8] [5 1] .

[3] height is 1 0 m or more 1 0 cm less aligned single-walled carbon nanotube bulk according to any one of obtaining a Parc structure from the above [4 8] shall be the Toku徵 [5 2] method of manufacturing the structure.

Orientation of any crab described to control the growth of the probe from the [4 8] to Toku徵 [3] - [5 4] the shape of the bulk structure Pas evening-learning of the metal catalyst and carbon nano Ju method for producing a single-layer forces one carbon nanotube bulk structure.

[5 5] After the Parc structures grown, the catalyst also not exposed to the solution and the solvent of any one of [4 8], characterized in that it can be separated from the substrate [5 4] method for producing aligned single-walled carbon nanotube bulk structure.

[5 6] purity aligned single-walled carbon nanotubes according to any one of the above [4 8] to Toku徵 of [5 5] to obtain a Parc structure is 9 8 mass% or more - preparation of Parc structure Method.

[5 7] the production method of the aligned single-walled carbon nanotube Parc structure according to any one of purity from above [48], characterized in that to obtain a bulk structure is 9 9 mass% or more [56].

[58] fabrication of aligned single-walled force one Bon'nanochu Bed bulk structure according to the purity obtain Parc structure is 99. 9mas s% or more from the [48] to Toku徵 any one of [57] Method.

[59] fabrication of aligned single-walled carbon nanotubes Parc structure according to any one of the above [48] the specific surface area and obtaining a bulk structure is 600 meters 2 / g or more [58] Method.

[60] aligned single-walled carbon nanotube bulk structure according to any one of the specific surface area to obtain a 800 m 2 / g or more 2000 m 2 / g or less is bulk structure from the [48] to Toku徵[59] method of manufacturing the body.

[61] aligned single-walled carbon nanotube bulk structure according to any one of the specific surface area to obtain a Parc structure is less than 1000 m 2 Zg least 2000 m 2 Zg from the [48] to Toku徵the [60] the method of production.

[62] The specific surface area is from the [48], wherein the obtaining a bulk structure made of unopened monolayer force one carbon nanotube is not more than 600 meters 2 / g or more 1300 m 2 / g to any one of [58] method for producing aligned single-walled carbon nanotubes' Parc structure according.

[63] The specific surface area is from the [48], wherein the obtaining Parc structure consisting of unopened monolayer force one carbon nanotube is not more than 800 m 2 / g or more 1200 m 2 / g [58], [62] method for producing aligned single-walled carbon nanotubes' Pal click structure according to any one of.

[64] specific surface area according to any one of the above [48] to Toku徵to obtain a 1600 m 2 / g or more 2500 m 2 / g consisting of at which the opening monolayer force one carbon nanotube following Parc structure [58] method for producing aligned single-walled carbon nanotubes' Parc structure.

[65] that the specific surface area to obtain a Parc structure consisting opening monolayer force one carbon nanotube is not more than 1800 m 2 Zg least 2300 m 2 / g from the [46] to Toku徵[5 8], [6 4] method for producing aligned single-walled carbon nanotubes' bulk structure according to any one of.

[6 6] orientation and optical properties in a direction perpendicular thereto, electrical properties, mechanical properties, to obtain a pulse click structure having at least anisotropy in one of the magnetic characteristics Contact Yopi thermal properties any method for producing aligned single-walled carbon nanotube bulk structure according to the above from [4 8] [6 5] to Toku徵 a.

1 [6 7] the size of the alignment direction perpendicular to the direction of anisotropy in it, relative to larger value is the lesser value: the to Toku徵 to obtain the Parc structure is 3 or more

[6 8] the size of the alignment direction anisotropy in a direction perpendicular thereto, 1 to the value of the lesser value larger: the to Toku徵 to obtain a 5 or more at a bulk structure

[6 6] or [6 7] the production method of the aligned single-walled carbon nanotube Parc structure according to.

[6 9] the size of the alignment direction perpendicular to the direction of anisotropy in it, one for the value of the lesser value larger: and Toku徵 to obtain the Parc structure is 1 0 or more the above

Method for producing aligned single-walled force one carbon nanotube Pal click structure according to any one of [6 6] to [6 8].

[7 0] production how the aligned single-walled carbon nanotubes' Parc structure according to any one of the above [4 8] [6 9] to Toku徵 the orientation in a predetermined direction is vertical alignment.

[7 1] above single-walled carbon nanotube according to any one of [1] to [1 1] or the aligned single-walled carbon nano Ju over according to any one of [2 8] [4 7] Bed, & the Parc structures, devices der connexion be separated from at least one of the substrate and the catalyst, separation device to Toku徵 further comprising cutting means or suction means.

[7 5] the single-walled carbon nanotube according to any one of [1] to [1 1] or the aligned single-walled carbon nano Ju over according to any one of [2 8] [4 7] Bed, & heat radiator to Toku徵 for using the Parc structure.

[7 8] requires heat dissipation, electrical products, article according to [7 7] to Toku徵 the electronic products, is at least one selected from optical products, and mechanical products. [7 9] the single-walled carbon nanotube according to any one of [1] to [1 1] or aligned single-walled carbon nano Ju over according to any one of the above [2 8] [4 7] Bed, & heat conductor, characterized in that using a bulk structure.

[82] it requires heat transfer, electrical products, article according to [81] above, Toku徵 the electronic products, is at least one selected from optical products, and mechanical products. [8 3] the monolayer force one carbon nanotube according to any one of [1] to [1 1] or aligned single-walled force one Bon'nanochu over according to any one of the above [2 8] [4 7], conductor characterized by using a blanking bulk structure.

Composite material to Toku徵 by containing a conductor according to [8 4] above [8 3]. Article to Toku徵 further comprising a conductor according to [8 5] above [8 3].

[8 8] wiring lines according to [8 7] to Toku徵 that the peer wiring. [8 9] above [8 7] or child part conductive to Toku徵 further comprising a wire according to [8 8]. [9 0] the single-walled carbon nanotube according to any one of [1] to [1 1] or aligned single-walled carbon nano Ju over according to any one of the above [2 8] [4 7] Bed, & optical element characterized by using a Parc structure.

[9 1] optical element according to [9 0], wherein the optical element is a polarizer.

[9 3] above [9 0] or optical article shall be the Toku徵 further comprising an optical element according to [9 1].

[9 4] the single-walled carbon nanotubes according to any one of [1] to [1 1] or the from [2 8] according to any one of [4 7] aligned single-walled carbon nano Ju, - Bed & reinforcement to Toku徵 for using the Parc structure.

[9 5] reinforcement according to [9 4] to Toku徵 that the single-walled carbon nanotubes or aligned single-walled carbon nanotube Pal click structure was a laminate.

Composite material shall be the Toku徵 by containing reinforcing material according to [9 6] above [9 4] or [9 5].

[9 7] metal composite material according to the substrate and to Rukoto at least one selected from ceramics and resin to [9 6] to Toku徵.

[9 8] the monolayer force one carbon nanotube according to any one of [1] to [1 1] or aligned single-walled carbon nano Ju over according to any one of the above [2 8] [4 7], electrode material characterized by using a blanking bulk structure.

Composite material characterized by containing an electrode material according to [9 9] above [9 8]. [1 0 0] cell, characterized in that the electrode material according to the electrode to [9 8]. [1 0 1] battery, battery according to [1 0 0] to Toku徵 is at least one selected from the secondary batteries, fuel cells and air cells.

[1 0 2] the single-walled carbon nanotubes according to any one of [1] to [1 1] or aligned single-walled carbon nanotube of any one of [2 8] to [4 7], Parc structure the is characterized in that an electrode material or a constituent material wire carrier Pasi evening or supercapacitors sheet evening.

[1 0 3] aligned single-walled carbon nano Ju according to any one of the single-walled carbon nano Ju one-flop according to any one of [1] to [1 1] or from [2 8], [4 7] an electron emission element characterized by using chromatography Bed Parc structure.

[1 0 4] the field emission display to Toku徵 further comprising an electron-emitting device according to [1 0 3].

[1 0 5] the monolayer force one Bon'nanochu Bed according to any one of [1] to [1 1] or aligned single-walled force one Bon'nano according to any one of [4 7] from the [2 8], adsorbent to Toku徵 for using the tube Parc structure.

[1 0 6] the single-walled carbon nanotubes according to any one of [1] to [1 1] or aligned single-walled carbon nanotube of any one of [2 8] to [4 7], gas occlusion body to Toku徵 to that used bulk structure.

Single-walled carbon nanotubes of the invention of a [1 1] from the [1] This application as described above is mixed such as catalyst or by-products is suppressed as compared with the conventional single-walled carbon nanotubes, highly purified, which has been high specific surface area of, which is extremely useful in nanoelectronic devices, application to nano-optical devices, energy storage, and the like. .

Further, according from the [1 2] of this application to the method of the invention of a [2 7], by an extremely simple means of addition to the reaction system in which the oxidant steam, the first [1] or al the in addition to monolayer force one carbon nanotube of the invention [1 1] can be produced, it can be produced also multi-walled carbon nanotubes having similar excellent properties. Moreover, to extend the life of the metal catalyst, realize the growth of efficient carbon nanotubes at a high growth rate, easily stripped on it is possible to mass production, the carbon nanotubes grown on the substrate from the substrate or the catalyst also to become can be.

Also, aligned single-walled carbon Nanochi Yubu Parc structures invention from the [2 8] of this application of the [4 7] A plurality of collectively are aligned single-walled carbon nanotube electrical and electronic or optical has a functionality of equal, contamination such as catalyst or by-products is suppressed, high purity, having been high specific surface area of, yet greatly be large-scaled also its height, nanoelectronic devices, other applications of the nano-optical devices, energy storage, etc., a variety of applications can be expected. Moreover, those formed by patterning of one of the aligned single-walled carbon nanotube Parc structure of the invention of this application, which has achieved the first patterning of a collection of single-walled carbon Nanochi Yubu, this stuff this those that did not exist until, in the same manner as described above nanoelectronic devices, other application to nano-optical element and energy storage, etc., a variety of applications can be expected.

Furthermore, according from the [4 8] of this application to the method of the invention of a [7 0], by an extremely simple means of addition to the reaction system of water vapor, the from the first [2 8] [4 7] it is as possible out to produce the aligned single-walled carbon nanotube 'bulk structure of the invention. Moreover, to extend the life of the metal catalyst, realize the growth of efficient aligned single-walled carbon carbon nanotubes' Parc structure at a high growth rate, grown aligned single-walled carbon nano tube Parc structure from the substrate or the catalyst also to become capable of easily peeling.

Further, according to the separation apparatus of the [7 1] This application can be separated very simply board or touch SWNTs in particular aligned single-walled carbon nanotubes from the medium, the Parc structure body.

Further, according to the method of the invention of the [7 2] or [7 3] of this application, without causing long deactivating the catalyst and the single-walled carbon nanotubes and single-walled aligned carbon nanotube is produced to a high efficiency it can, moreover, oxidation by oxidizing agents - not burning only, chemical etching, plasma, ion milling, microwave irradiation, on which may be employed a wide variety of processes, such as ultraviolet radiation, vapor phase, liquid since none of the processes of the phases can be employed, with significant benefits flexibility in selection of the manufacturing process is one had been high whole.

Furthermore, the apparatus according to the invention of a [7 4] of this application, yet simple structure, it is possible to mass-produce the single-walled carbon nanotubes and single-walled aligned force one carbon nanotube with high efficiency.

Furthermore, according from the [7 5] of this application to the invention of a [1 0 6], heat radiator, heat Netsutai, conductors, optical elements, reinforcement, the electrode material, battery, Capacity evening or super one capacitor the electron emission device, the adsorbent, other application to gas storage body or the like, various applications can be realized. BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a schematic view of the separation apparatus used the aligned single-walled carbon nanotube bulk structure to separate from the substrate or the catalyst.

Figure 2 is a schematic view of the separation apparatus used the aligned single-walled carbon nanotube Parc structure to separate from the substrate or the catalyst.

Figure 3 is a graph showing the height relationship of the water addition amount and the aligned single-walled carbon nanotube Parc structure.

4, the water amount and the aligned single-walled carbon nanotube height is a graph showing the relationship between catalyst activity and catalyst life.

Figure 5 is a diagram table the state of deactivated catalyst by secondary products observed by an electron micrograph.

3 0 shows an enlarged photograph of a vertically aligned single-walled carbon nanotube bulk structure body was peeled off from the substrate, those dispersed in an aqueous solution was guessed seen by electron microscopy (TEM) produced in Example 2 it is a diagram.

Figure 3 represents a single-walled carbon nano Ju of as-gr own prepared in conventional CVD method - is a view similar to FIG. 3 0 of the probe.

3 2 is a diagram showing a result of the vertically aligned single-walled carbon nanotube bulk structure body prepared in Example 2 was thermogravimetric analysis.

Figure 3 3 is a diagram showing a photographic image showing the state of the vertically aligned single-walled carbon nanotube Parc structure before peeling taken with a digital camera.

3 4 is a view similar to FIG. 3 3 after peeling.

3 5, the as placed in exfoliated containers - is a view showing a single layer of gr own carbon nanotube product.

4 7 is a measured value of the charge and discharge characteristics of a super-one Capacity evening obtained in Example 6. 4 8 is a graph of charge-discharge characteristics of the lithium battery obtained in Example 7.

4 9 is a graph showing the adsorption and desorption isotherms of the aligned single-walled force one carbon nanotube Pas torque structure of Example 2 was measured in Example 8.

5 0 is a graph showing polarization dependency of the light transmittance of the aligned single-walled carbon nanotube Parc structure as a polarizer in Example 9.

5 1 is a graph showing polarization dependency of the light absorption rate of the aligned single-walled carbon nanotube Parc structure used in Example 9.

5 3 is a graph showing measurement data of the thermal diffusivity of the aligned single-walled carbon nanotubes' Pal click structure as a radiator of Example 1 1.

5 4, aligned single-walled carbon nanotubes as a conductive material of Example 1 2 is a graph showing the electrical transport properties of Pal click structure. BEST MODE FOR CARRYING OUT THE INVENTION

While the invention of this application has the Toku徵 of as described above, it will be described embodiments thereof hereinafter.

First, we describe SWNTs invention of a [11] from the [1] of the present application.

Single-walled carbon nanotubes of the invention of this application, purity 98ma ss% or more, preferably 99ma ss% or more, more preferably to Toku徵 the Der Rukoto 99. 9 mA ss% or more.

Here, the purity referred to in this specification are expressed in mass% of the carbon nanotubes in the product (ma ss%). Measurement of such purity is measured by elemental analysis using fluorescence X-rays.

The single-walled carbon nanotubes, for example, can be produced by the method of the invention of a [27] from the [12] described above. The single-walled carbon Nanochi Interview part obtained are those high purity as described above. Its purity is 98ma ss% or more, preferably 99ma ss% or more, more preferably 99. 9 mA ss% or more. When not performing the purification process, the purity of immediately after growth (a s-grown) is the purity of the final product. If necessary, it may be subjected to purification treatment.

Moreover, single-walled carbon nanotubes of the invention of this application has a specific surface area of 600 meters 2 Zg least 1300 m 2 / g or less, more preferably 600 meters 2 Zg least 1300 m 2 / g or less, more preferably 800 m 2 / g or more 1200 m 2 Zg less are either those of the primitive port, or a specific surface area of 1600 m 2 / g or more 250 OmVg less, more preferably 1600 m 2 / g or more 2500 m 2 Zg hereinafter further rather preferably is 180 On ^ Zg least 2300 m 2 / g is obtained by following the opening. Since such a very large specific single-walled carbon nanotubes having a surface area also been no are those obtained for the first time by the inventors of this application.

Further, the single-walled carbon nanotubes can be provided with aligned, favored properly can be provided with vertically aligned on a substrate. Single-walled carbon nanotubes oriented vertically by the inventor of this application, contamination such as a catalyst and by-product formation was is suppressed, one which is highly purified, the purity of the final product is intended not to Until now . Moreover when grown on the substrate can be easily peeled off from the substrate or the catalyst.

As a method for peeling the single-walled carbon nanotubes, physical, chemical there have is a way to peel from mechanically substrate, for example an electric field, a magnetic field, centrifugal force, a method for peeling using surface tension; mechanical direct method stripped from the substrate; pressure, and a method of peeling from the substrate using a heat can be used. A simple peeling method, directly from the substrate by tweezers, knob, there is a method of peeling. More preferably, it may be separated from the substrate using a thin blade such as a cutlet evening one blade. The Is Raniwa, vacuum pump, with a vacuum cleaner, suction from the substrate, it is also possible to strip. Further, after peeling, the catalyst is residual on the substrate, it is possible to grow a single-walled carbon nanotubes vertically aligned using it newly.

Therefore, such a single-walled carbon nanotubes are extremely useful in nanoelectronic devices, application to nano-optical devices, energy storage, and the like.

Incidentally, a representative example of an apparatus for peeling and separating a single-walled carbon nanotubes from the substrate or the catalyst schematically in FIGS.

Next, the process for producing the carbon nanotubes invention from the [1 2] This Application No. [2 7].

These inventions, a shall involved in a method for producing carbon nanotubes by a CVD method, Toku徵 that as its requirement for the presence of a metal catalyst to the reaction system, and adding an oxidizing agent to the reaction atmosphere It is set to.

As the carbon compound as a raw material carbon source, as in the conventional, hydrocarbons, among them lower hydrocarbons such as methane, Etan, propane, ethylene, propylene, § acetylene and the like are usable as suitable. These may be of the one or two or more kinds, as long as acceptable conditions for the reaction, methanol, lower alcohols Ya Aseton, low carbon number oxygenated fluorinated case of such carbon monoxide, ethanol, etc. the use of things is also taken into consideration. Ambient gas of the reaction does not react with the carbon nanotube, if the growth temperature inert, can be used, such as those, helium, argon, hydrogen, nitrogen, neon, krypton, carbon dioxide, such as chlorine or gas mixture thereof can be exemplified, in particular helium, argon, hydrogen, and mixtures of these gases preferred. Atmospheric pressure in the reaction so far as long as the pressure range which carbon nanotubes are produced, can be applied to, 10 3 or more 10 7? & Preferred (100 atmospheric pressure) or less, 10 4 Pa or more 3X10 5 Pa ( 3 atmospheric pressure) more preferably less, particularly preferably 5 Xl OPa more 9X10P a less.

The reaction system, but the presence of said as the metal catalyst, as this catalyst, it is possible to use those appropriately as long as it is used in the production of carbon nanotubes Until now, for example, iron chloride thin iron films made with evening sputtering, iron - mode Ribuden thin film can be exemplified alumina ferrous film, alumina one Kozoruto film, an alumina ferrous one mode Ribuden thin film or the like.

The amount of catalyst present, so far can be used in that range if Re quantity der which carbon nanotubes are prepared, for example, in the case of using the iron metal catalyst, the thickness Saga 0. 1 nm or more 100 the following are preferred nm, preferably La 0.5 on 5 賺以 5 nm or less is, and particularly preferably 2nm or more lnm.

Placement of the catalyst can be used sputtering evening vapor deposition appropriate method as long as it is a method to arrange a metal catalyst with the thickness as described above. Further, Ru can also simultaneously producing a large number of single-walled carbon nanotubes by using a putter-learning of the metal catalyst to be described later.

Temperature during the growth reaction in CVD, reaction pressure, temperature as the metal catalyst, but suitably determined by considering the kind of the raw material carbon source and acid agent, the effect of addition of the oxidizing agent is expressed enough it is desirable to set the range. The most preferred temperature range is a lower limit value, and temperature etc. catalyze the secondary product is inactivated, for example, amorphous carbon or graphite layer is removed by an oxidizing agent, the upper limit value, the main raw Narubutsu, for example carbon nanotubes it is to a temperature which is not oxidized by the oxidizing agent. Specifically, in the case of water, preferably to 100 Ot inclusive at 600, yet it is effective to less 6 5 0 or 9 0 0. In the case of oxygen, the 6 5 0 less preferably 5 5 0 from the following, or less 1 2 0 0 In the case of carbon dioxide, more preferably it is effective to or less 1 1 0 0 . Then, addition of an oxidizing agent which is one of Toku徵 of the invention of this application increases the activity of the catalyst during CVD growth reaction and the effect of prolonging the activity life. The synergistic effect, as a result, the carbon nanotubes to be generated is greatly increased. Oxidizer 3 and (water) amount shows the activity of the catalyst, a graph quantitatively evaluate the life (catalyst: iron thin film; starting material gas: ethylene). Ri by the addition oxidant (water) vapor, considerably the activity of the catalyst becomes high, and mowing Kotogawa the life of the catalyst is extended. Without the addition of moisture, and the catalyst activity, the catalyst life is indeed quantitatively evaluate child and is extremely difficult, decreases.

It shows an example of the relationship between the oxidizing agent (water) amount and vertically aligned single-walled carbon nanotubes' Parc structure of the height (the amount of single-walled carbon nanotubes) in FIG. By adding an acid agent (water), it can be seen that the vertically aligned single-walled force one carbon nanotube, the height of Pal click structure increases significantly. This indicates that Ri by the addition oxidant (water), single-walled carbon nanotubes are more efficiently produced. Catalytic activity by adding an oxidizing agent (water), the life of the catalyst, and that its height increases markedly properly as a result, one of the most important feature of the invention of this application. The Rukoto to adding an oxidizing agent, the finding that the height of the vertically aligned single-walled carbon nanotube bulk structure is greatly increased, is to before this application it is completely unknown, the inventors of this application for the first time found a landmark thing was by the like.

The function of the oxidizing agent added in the invention of this application, there is no uncertain at present, is considered as follows.

In normal force one carbon nanotube growth process, the catalyst is covered with secondary products produced during the growth such as amorphous force one carbon or graphite layer during growth, the catalyst activity decreases, the life is shortened, rapidly deactivated. 5 shows a high-resolution electron microscope image of the grown missed catalyst carbon nanotubes. Grown missed catalyst carbon nanotubes are covered with secondary products that occur during growth, such as Subekaraku amorphous carbon or graphite layer. When secondary products cover the catalyst the catalyst is deactivated. However, when the oxidizing agent is present, secondary products produced during the growth such as amorphous carbon or graphite layer is converted like is oxidized CO gas, removed Ri taken from the catalyst layer, Thus, the catalyst activity is enhanced, the catalyst lifetime is also prolonged, as a result, the growth of the carbon nanotubes progresses efficiently, and estimated that the vertically aligned single-walled carbon nanotube 'bulk structure whose height is remarkably increased to obtain ing.

The oxidizing agent, water vapor, oxygen, ozone, hydrogen sulfide, acid gas also, mixing a lower alcohol, carbon monoxide, low carbon number of oxygen-containing compounds such as carbon dioxide and of these, such as E evening Bruno Lumpur, methanol gas is also effective. Among these, water vapor, oxygen, carbon dioxide, preferably carbon monoxide, in particular water vapor is preferably used. The addition amount is not particularly limited and may be a small amount, for example in the case of water vapor, usually, l O p pm or l OOOO p pm or less, more preferably 5 0 p pm or 1 0 0 0 p pm or less, more preferably Ru der following 2 0 0 p pm or 7 0 0 p pm. The addition amount of the case from the point of view of improving the catalytic activity by preventing degradation and water vapor addition of a catalyst of the water vapor in the range described above is preferable.

The addition of this oxidant, sustained carbon Nanochi Interview growth of some dozens minutes to at most completed in about 2 minutes in a conventional growth rate 1 0 0 times or more than the conventional one in the further 0 also it will increase to 0 0 times.

In the method of the invention for application, but a single layer and can it to produce a multilayer force one carbon nanotube, particularly effective for the production of single-walled carbon nanotubes. Therefore, in the following is described the single-walled carbon nanotube is the same for multi car carbon nanotubes.

In the method of the invention of this application, the catalyst can be grown single-walled carbon nanotubes oriented vertically to the substrate surface disposed on a substrate. In this case, as the substrate, so far is a use available-ones appropriate as long as the carbon nanotubes are prepared, may be mentioned for example, as follows.

This height of the vertically aligned single-walled carbon nanotubes produced by the method of the invention of application (length) is different from the preferred range depending on the application, rather preferably the lower limit is 10 / ΛΠΙ, more preferably 20 m, particularly preferably 50 m, there is no particular limitation on the upper limit, from the viewpoint of practical use, it is preferably 2. 5 mm, preferably in the al lcm, particularly preferably 10 cm.

The single-walled carbon nanotubes produced by the method of the invention of application is significantly Naru difference there Ru and single-walled carbon nanotubes manufactured by the conventional CVD method have you to its purity. That is, the single-walled carbon nanotubes manufactured by the method of the invention of this application, 98ma ss% or more, preferably 99ma ss% or more, and more preferably from 99. 9 mas s% or more purity. Moreover when grown on the substrate can be easily peeled off from the base plate or the catalyst. The method and apparatus for peeling the single-walled carbon nanotubes, the method described above is employed.

Single-walled carbon nanotubes manufactured by the method of the invention, may be subjected to conventional same purification treatment as required.

Further, the single-walled carbon nanotubes produced by the method of the invention, specific surface area is 600 meters 2 / g or more 1300 m 2 Zg less, more preferably 600 meters 2 / g or more on 1300 m 2 Zg or less, more preferably 800 m 2 / or g or 120 OmVg is below those of the non-opening, or a specific surface area of 1600 m 2 / g or more 2500 m 2 / g or less, more preferably 1600 m 2 / g or more 2500 m 2 Zg hereinafter, more preferably 1800m 2 / g or more 2300m and 2 / g or those following the opening, and has a very large specific surface area.

In the method of the invention of this application, requires a means for supplying an oxidizing agent, the reaction apparatus for the C VD method, construction of the reactor are not particularly limited structure. Specific embodiments will be described later.

Next, we describe aligned single-walled carbon Nanochi Interview some bulk structure of the invention from the [2 8] This Application No. [4 7].

Aligned single-walled carbon nanotube Parc structures invention from the [2 8] This Application No. [4 7] comprises a plurality of aligned single-walled carbon nanotubes, and characterized in that the height 1 0 im more it is intended to.

The "structure" in the specification of this application, those oriented single-walled carbon nanotubes gathered plurality of electrical 'electronic, it is to perform the function of the optical and the like. The aligned single-walled force one carbon nanotube 'bulk structure can be manufacture for example by the method of the invention of a [7 0] and the [7 2] to [7 3] from the [4 8] described above .

The aligned single-walled carbon nanotube Parc structures purity 9 8 mass% or more, more preferably 9 9 mass% or more, particularly preferably 9 9. 9 mass% or more. When not performing the purification process, after the growth - purity in (as gr own) is the purity of the final product. If necessary, it may be subjected to purification treatment. The aligned single-walled carbon nanotube 'bulk structure Ki de be those predetermined orientation, preferably be provided with vertically aligned on a substrate.

Its preferred range is different depending on the application for the height (length) of the aligned single-walled force one carbon nanotube Parc structure of the invention of this application, when used as also the large scale of the lower limit is preferably 1 0 / m, more preferably 2 0 a m, particularly preferably 5, the upper limit is preferably 2. 5 mm, more preferably lcm, particularly preferably 1 0 cm.

Thus, aligned single-walled carbon nanotube Parc structure Zotai by the inventor of this application, was suppressed contamination such as catalyst or by-products, which is highly purified, the purity of the final product are those not so far. Also, aligned single-walled carbon nanotubes' Parc structure according the invention of this application, the the height is also intended to greatly is large scaled, as described later, nano electronic devices, nano-optical devices, energy storage, etc. other applications of to, a variety of applications can be expected.

Also, aligned single-walled carbon nanotube Parc structure of the invention of this application is the specific surface area is extremely large, but the preferred value varies depending on the application, in the case of large specific surface area is desired applications, 600 meters 2 Zg or more, more preferably 80 Om 2 / g or more 2500 m 2 Zg or less, more preferably 1000 m 2 Zg least 2300 m 2 / g or less. Moreover, single-walled carbon nanotube Pal click structure of the invention of this application, the apparatus having the unopened, specific surface area of 600 meters 2 Zg least 1300 m 2 / g or less, more preferably 600 meters 2 / g to 130 om 2 Zg, and more preferably not more than 800 m 2 / g or more 1200 m 2 Zg. Furthermore, single-walled carbon nanotube Parc structure of the invention of this application, the apparatus having having an opening, a specific surface area of 1600 m 2 Zg least 2500 m 2 / g or less, more preferably 1600 m 2 / g or more 2500 m 2 / g or less, still more preferably not more than 1800 m 2 Zg least 23 00m 2 Zg. Such very large specific single layer carbon nanotubes have a surface area 'bulk structure intended been no, it was collected using first order by the inventors of this application.

Measurement of the specific surface area can be performed by measuring the adsorption-desorption isotherms. As its one example, aligned single-walled carbon nanotube bulk structure just after generation (a sg r own), the adsorption-desorption isotherm of liquid nitrogen 30 milligrams 77 using BELSORP-MINI Ltd. 曰本 Bell It was measured (adsorption equilibrium time was 600 seconds). All adsorption amount showed an extremely large numerical (165 OmVg) (see FIG. 6). Was measured specific surface area from the adsorption and desorption like temperature line was 110m 2 / g. The 0.5 below and linearity of the adsorption and desorption, etc. 撣線 is obtained at a relative pressure region, it can be seen carbon nanotubes aligned single-walled carbon nanotube Parc structure in the fact that it is unopened.

Also, aligned single-walled carbon nanotube bulk structure according to the invention of the present application, For example other as shown in the following Example 8, by performing opening processing, the tip portions are open mouth, a specific surface area more it can be made that increased. In Example 8, thereby realizing an extremely large specific surface area as 2 0 0 0 m 2 / g . The aperture processing, as the de dry process, it is possible to use a treatment with oxygen. Wet when pro cell scan can be used, the treatment with an acid, in particular the reflux processing and with hydrogen peroxide, may be used a cutting process or the like at high temperature hydrochloric acid. The aligned single-walled carbon nanotube 'bulk structure which has been subjected to the opening process shows the Oite convex isotherms 5 following relative pressure region 0.5 (see FIG. 4 9). It can be seen that aligned single-walled carbon emissions force one carbon nanotube in the nanotube bulk structure in is opened from it.

Noteworthy Therefore, in the state immediately after generation aligned single-walled carbon nanotube bulk structure according to the invention of this application, also in the post-aperture processing, among monolayer force one carbon nanotube that has been reported in the past hunt that has the highest specific surface area is minute.

Therefore, the specific surface area compared with that aligned single-walled carbon nanotube bulk structure Zotai is conventional according to the invention of this application since it is very large, the heat dissipating body, electrode materials, super one capacitor, fuel cell, the adsorbent , Phil evening one, Akuchiyue one coater (artificial muscle), sensors, humidity control agent, is extremely promising as a heat retaining agent, and the like. Also, it aligned single-walled carbon nanotube Parc structure according to the invention of this application, since it has orientation, the optical properties orientation direction perpendicular thereto, electrical characteristics, mechanical characteristics, magnetic characteristics and shows the anisotropic at least one of thermal anisotropy. The degree of anisotropy of the single-walled carbon nanotube Parc orientation direction of the structure and perpendicular thereto direction is preferably 1: 3 or more, more rather preferably is 1: 5 or more, particularly preferably 1: 1 is greater than or equal to zero. The upper limit is 1: 1 0 0 about. Such a large anisotropy, for example, in the case of optical properties, to allow application to a polarizer using the polarization dependence of the optical absorptance or light transmission. For even anisotropy of other properties, heat exchangers utilizing their anisotropy, respectively, a heat pipe, and can be applied to various articles such as reinforcements.

Also, aligned single-walled carbon nanotube Parc structure of the invention of this application also have different heights of their showing a constant density. Normally, the value is converged to 0. 0 0 2~0. 2 g / cm 3, it can be controlled by controlling the density of the catalyst. 7, the height one weight of aligned single-walled carbon nanotube Parc structure, showing an example of a height one density curve. From FIG. 7, the weight of the aligned single-walled carbon nanotube bulk structure according to the invention of this application is increased in proportion to the height, also the density is the height of the aligned single-walled force one carbon nanotube 'Parc structure constant it is seen regardless (0. 0 3 6 g / cm 3).

Therefore, it aligned single-walled carbon nanotube Parc structure body according to the invention of this application is a very homogeneous material, heat dissipation sheets, heat transfer sheet, is a response as a heat exchanger is expected.

Further, in the above example of the single-walled carbon nanotube Parc structure according to the invention of this application, by the electron microscopic observation, a very high value of content of single-walled carbon nanotubes (filaments) of 9 9.5% or more It was those.

Further, those containing a high quality monolayer force one carbon nanotube (Fuiramen Bok) the aligned single-layer carbon nanotube Nono Rireku structure of the invention of this application. Quality of aligned single-walled carbon nanotubes' Parc structure in the single-walled carbon nanotubes (filaments) can be evaluated by measuring the Raman spectroscopy. An example of evaluation of Raman spectroscopy shown in FIG. From Figure 8, observed in the G band is 1 5 9 2 Kaiser with a sharp peak, it can be seen that the graphite crystal structure is present. Further, D band than smaller, fewer defects, it can be seen that high-quality good graphite layer is present. Further, in the low wavelength side, R BM mode is observed due to the plurality of single-walled carbon nanotubes, graphite layer is seen Oh Rukoto in monolayer force one carbon nanotube. From these, high-quality single-walled carbon nanotubes of the present child was found in aligned single-walled carbon nano tube 'bulk structure in which according to the invention of this application.

Furthermore, the size of the single-walled carbon nanotubes aligned single-walled carbon nanotube bulk structure in the invention of this application (filament) is from 0.8 to 6 showed a broad support I's distribution of nm, also the center size l~ is 4 nm. Size distribution, the center size can also be controlled by preparing the catalyst.

Size distribution evaluation of the single-walled carbon nanotubes (filaments) can be is carried out by high-resolution electron microscope. That is, by measuring the size of one single single-walled carbon nanotubes from the electron microscopic photograph, a histogram, it is possible to calculate the size distribution from the histogram created. An example of the size distribution evaluation are shown in FIG. Monolayer force one carbon nanotube aligned single-walled carbon nanotube bulk structure in FIGS. 9 shows a broad size distribution of 1 to 4 nm, also the center size was confirmed to be 3 nm.

The size distribution is centered size 1 nm of single-walled nanotubes made by conventional H i ​​P co method, also when compared to 1. 5 nm of the produced monolayer force one Bon'na Bruno tube by laser ablation over Chillon method it has been found is extremely large. Large tube size large interior space, conventionally ivy it impossible enclosing it becomes possible for encapsulating biomolecules such as DNA, DNA that is those very highly useful as a new composite material.

Note that this aligned single-walled carbon nanotube Parc structure may be in a range that does not impair inhibitory their function, to encompass double-walled carbon nanotubes and more multi-walled carbon nanotube. Also, aligned single-walled carbon nanotube Parc structure of the invention of this application may be assumed that the shape of that is Pas evening-learning into a predetermined shape. An aggregation of a plurality of aligned single-walled carbon nanotubes, the shape is not present so far what is patterned into a predetermined shape, is the first to realize the invention of this application. The shape of patterning of the other thin-film can be cylindrical, such as those in which the prismatic, or complex shape, and of various shapes. This path evening-learning of can be controlled in a manner described below.

Next, the process for producing the aligned single-walled carbon Nanochi Interview some bulk structure of the invention from the [4 8] This Application [7 0].

The method of the invention, aligned single-walled carbon nanotubes by C VD method - one related to a method of manufacturing a bulk structure, as is the requirement, by patterning the metal catalyst on a substrate, the presence of a metal catalyst is a Toku徵 Upon, adding an oxidizing agent to the reaction atmosphere a plurality of single-walled carbon nanotubes so that you oriented in a predetermined direction by a chemical vapor deposition (CVD) and structures with respect to the substrate surface under . In this case, it will be mainly described a case of patterning the aligned single-walled carbon nanotube bulk structure. A schematic of the steps of the manufacturing method shown schematically in Figure 1 0. As the carbon compound as a raw material carbon source, as in the case of the first [1 2] of inventions of the [2 7], hydrocarbons, among them lower hydrocarbons such as methane, Etan, propane, ethylene, propylene , acetylene and the like are usable as suitable. These may be of more than one or two, as long as acceptable conditions for the reaction, methanol, use of lower alcohols and acetone, a low number of carbon atoms of oxygen-containing compounds such as carbon monoxide, ethanol, etc. also it is taken into account.

Ambient gas of the reaction does not react with the carbon nanotube, if the growth temperature inert, can be used, such as those, helium, argon, hydrogen, nitrogen, neon, krypton, carbon dioxide, such as chlorine or gas mixture thereof can be exemplified, in particular helium, argon, hydrogen, and mixtures of these gases preferred. Atmospheric pressure in the reaction, if the pressure range in which carbon nanotubes have been produced so far, can be applied to, preferably 1 0 & Up 1 0 & (1 0 0 atmospheric pressure) or less, 1 0 4 P a more more preferably 3 X 1 0 5 P a ( 3 atmospheric pressure) or less, particularly preferably less 5 XIOP a higher 9 X 1 0 P a.

The reaction system, but the presence of said as metal catalyst, the metal catalyst, heretofore can be used and the appropriate as long as it is used in the production of carbon nanotubes, such as iron thin film chloride iron thin film fabricated in evening sputtering, iron one molybdenum thin film, alumina ferrous film, alumina - cobalt thin film, alumina - iron - can be exemplified molybdenum thin film or the like.

The amount of catalyst present, so far can be used in that range if Re quantity der which carbon nanotubes are prepared, for example, in the case of using the iron metal catalyst, the thickness Saga 0. 1 nm or more 1 0 0 nm or less, preferably to 0. 5 nm or more 5 nm or less is al, and particularly preferably 2 nm or more 1 nm. Presence area of ​​the catalyst can be arbitrarily set according to the size of the structure you produce.

Patterning the patterning method of the catalyst, it is possible to use an appropriate method if directly or indirectly approach the catalytic metal can Patanin grayed may be a well-dry process at Uetsutopurosesu, for example, using a mask , Pa evening-learning using Nanoi down printing, putter training using software Bok lithography, patterning using printing, patterning using plated, patterning using screen printing, other patterning using lithography and foremost, the using any of the techniques of other materials catalyst on the substrate is selectively adsorbed by the putter-learning, the catalyst was selective adsorption to other materials, or a method of creating a pattern. A suitable procedure, patterning using lithography, metal deposition photolithography one using a mask, electron beam lithography, catalyst metal Pas evening-learning by the electron beam evaporation method using a mask, the catalytic metal by a sputtering method using a mask it is patterned.

For even substrate, it is possible to use the same kind of substrate as described in the case of the invention of a [2 7] from the first [1 2].

Temperature during the growth reaction of C VD method also may be selected the same temperature conditions as described in the case of the first [1 2] of the invention of a [2 7]. Then, as described above, the addition of the largest is one oxidizing agent, wherein the in the invention of this application increases the activity of the catalyst during the C VD growth reaction, also has the effect of extending the activity life.

This synergistic effect, as a result, it is possible to carbon nanotubes to be generated is greatly increased to obtain the vertically aligned single-walled carbon nanotube bulk structure body whose height is significantly increased. The addition amount may be a small amount is not particularly limited, varies depending on the production conditions, for example in the case of water vapor, usually, 1 0 p pm or 1 0 0 0 O p pm or less, more preferably 5 0 p pm or more 1 0 0 0 p pm or less, further preferred properly is less 2 0 0 p pm or 7 OO p pm. The addition amount of the water vapor from the viewpoint of improving the catalytic activity by preventing degradation and water vapor addition of a catalyst is in the range described above is preferable.

The addition of this oxidant, and most sustained carbon Nanochi Yubu growth of several tens of minutes to end in about 2 minutes in a conventional growth rate 1 0 0 times or more than the conventional, the further 1 0 0 0 also it will be increased to double.

Aligned single-walled carbon nanotube Parc structure manufactured in the method of the invention, there is remarkable Naru difference was the aligned single-walled carbon nanotubes Parc structure manufactured by a conventional C VD method in its purity. That is, manufacturing the aligned single-walled force one carbon nanotube 'Parc structure in the process of the invention of this application, purity 9 8 mass% or more, more preferably 9 9 mass% or more, particularly preferably 9 9. 9 mass % becomes more than a high-purity, yet when grown on the substrate can be easily peeled from the substrate or catalysts. As the separation method can be used the same procedure as described in the case of the invention of a [2 7] from the first [1 2].

The aligned single-walled carbon nanotube Parc structure Zotai produced by the method of the invention of application, may be subjected to conventional same purification treatment as required.

In the method of the invention of this application, the shape of the Parc structure can be arbitrarily controlled by the growth of the putter-learning and carbon nanotubes of a metal catalyst. An example of how to control the modeling of its 1 1.

This example is an example of a thin film Parc structure (structure Zotai relative diameter of the carbon nanotubes can be said that even thin film is Parc shape), the thickness is high, compared to the width thin and the width can be controlled to any length by the patterning of the catalyst, the thickness may be controlled to an arbitrary thickness by the patterning of the catalyst, the vertically aligned single-walled height constituting the structure body It has become can be controlled by the growth of carbon nanotubes. Sequence of the vertically aligned single-walled carbon nanotube in FIG 1 1 is summer as indicated by the arrow.

Of course, the shape of aligned single-walled carbon nanotubes' Parc structure produced by the method of the invention of this application is not limited to a thin film shape, a columnar shape, prismatic shape, or the like that a complicated shape, the catalyst patterning and the control of the growth can those with be Rukoto of various shapes.

Arrangement means for supplying the oxidizing agent is not particularly limited structure, For example other supplied as a gas or mixed gas, the supply of the vaporized oxidizing agent-containing solution, is vaporized and liquefied oxidant solid body supply of Te, supply by using an oxidizing agent atmosphere gas, supply utilizing spray, and high pressure, multiple supply, supply utilizing injection, supply utilizing a gas stream, and here methods utilizing a vacuum combined feed, and the like, Pabura and vaporizer, a mixer, stirrer, dilution device, sprayer, nozzle, pump, syringe, Konpuretsu service first class and, using a system that combines a plurality of these devices supply is taken. Also by accurately controlling very oxidant traces, in order to supply, the device may comprise a purifier that performs oxidant removal from the raw material gas carrier gas, for its, apparatus, supplying an amount of oxidant is controlled at a later stage to the raw material gas' carrier first gas which is removed oxidant in any manner described above. The above method is effective when the oxidizing agent to the raw material gas wire carrier rear first gas is contained in a trace amount.

Furthermore, in order to stably supply the oxidizing agent to accurately control device in that case by be equipped with a measuring device for measuring the concentration of the oxidizing agent, the oxidizing agent flow adjusting means the measured value to be fed packs may be performed more supply less stable oxidant change with time.

Furthermore, the measuring device may be filed with apparatus for measuring the synthesis amount of force one carbon nanotube, also, but it may also be a device for measuring the secondary products generated by the oxidizing agent.

Further, to synthesize large quantities of carbon nanotubes, the reaction furnace may be equipped with a substrate a plurality, or a system for continuously supplying and taking out. An example of a CVD apparatus which is suitably used to practice the method of the invention of this application is schematically shown in FIG. 1. 2 to FIG. 1 6.

Next, the process for producing the carbon nanotubes invention from the [7 2] of the Application [7 3].

The inventive method of application, secondary products to a process and catalyst for growing force one carbon nanotube is inactivated, for example, combines and amorphous carbon or graphite layer fracture Kowasuru step, under gas phase reaction or that under liquid phase it is a Toku徵.

The growth process, which means the crystal growth process of carbon nanotubes. Such growth step, the carbon nanotube production step of conventionally applied as it is. That is, the aspect of the growth process, none of the force one carbon nanotube production step of conventional use, for example, the raw material carbon source chemical vapor deposition (C VD) ​​carbon nanotubes to decompose at catalyst in the apparatus medium on aspects of growing, and the like.

And breaking step is, the force one carbon nanotube production process material Ru to deactivate the catalyst in secondary production of, for example, for example, such as amorphous carbon or graphite layer suitably eliminated, and the carbon nanotube itself does not exclude the process It means. Therefore, the Yabu壌 step, the catalyst in secondary production of carbon nanotube production steps can be employed both if the process to eliminate substances which inactivation, as such process, oxidizing agent oxidation by 'burning, chemical etching, plasma, I O Nmiringu, microwave irradiation, ultraviolet irradiation, can be exemplified quenching destruction of preferably the use of oxidizing agents, in particular the use of water is preferred.

The growth step and as the combination aspect of breaking step by performing the growth step and breaking step at the same time, the growth process and Yabu壌 steps are executed alternately, or a mode to emphasize growth step breaking step of emphasizing mode combine things like can and Ageruko.

As the apparatus for carrying out the method of the invention of this application, both above-mentioned apparatus can be used.

The combination of such steps, in the method of the invention of this application, the single-walled carbon nanotubes Contact Yopi single layer aligned carbon nanotubes, it is possible to manufacture the catalyst Kotonagu high efficiency to Nagatoki Mashitsukatsu , moreover, not only the oxidation and combustion by the oxidizing agent, chemical etching, plasma, ion milling, microphone port wave irradiation on UV irradiation, Ru can be employed a wide variety of processes, such as quenching destruction, the gas phase, from being able to adopt any of the process of the liquid phase, with a great deal of advantage was time and select the degree of freedom of the manufacturing process is increased.

Single-walled carbon nanotubes according to the invention of this application, a plurality of single-walled carbon Nanochi Yubu, is made of single-walled carbon nanotubes of 1 0 m or more aligned single-walled force one carbon nanotube Contact Yopi number double height, shape There has been and aligned single-walled force one carbon nanotube 'Parc structure patterned into a predetermined shape, ultra-high purity, super heat conductivity, high specific surface area, excellent electronic and electrical properties, optical properties, super mechanical strength, because they have different properties and characteristics, such as ultra-high density, it can be applied to various technical fields and applications. In particular, large scaled vertically aligned bulk structure and Patanin grayed, vertically oriented Parc structure Ru can be applied to the technical field as follows.

(A) heat radiator (heat dissipation characteristics)

Articles radiator is required, for example, computing power of the CPU is the heart of the electronic article computer heat generation rate becomes higher and higher, improved performance in the near future LSI from the CPU itself is required higher speed and high integration and we words when there is a possibility that the limit occurs. Conventionally, when the heat dissipation of such heat generation density, as heat radiator, while those of carbon nanotubes randomly oriented embedded in the polymer is known, there is a problem lacks heat release characteristics in the vertical direction . The large scaled vertically aligned force one carbon nanotube Parc structure according to the invention of this application, it shows a high heat radiation properties, moreover since it is obtained by vertically oriented high density and long, the ones When used as the heat dissipating material, may be compared to the conventional products enhance the heat radiation properties to dramatically vertically.

An example of this heat dissipating material is schematically shown in FIG 7.

Incidentally, the heat radiating body of the invention of this application is not limited to the electronic components, other various articles which heat dissipation is required, for example, electric products, can be take advantage as heat radiator, such as optical products, and mechanical products.

(B) heat transfer body (heat transfer characteristics)

Vertically aligned carbon nanotube Parc structure of the invention of this application has good heat transfer characteristics. Such excellent vertical alignment force on heat transfer characteristics one Bon'nanochu flop Parc structure With the heat transfer material is a composite material containing the same, it can be obtained a high thermal heat transfer conductive material, for example, heat exchanger vessels, dryers, when applied to the heat pipe or the like, it is possible to achieve the performance improvement. When such a heat transfer material was applied to the heat exchanger for aerospace, improvement in heat exchange performance, as possible out it is possible to reduce the weight 'volume. Further, such heat transfer materials of the fuel cell co-one-generation, when applied to a micro gas turbine, as possible out to improve the improved and heat resistance of the heat exchange performance. An example of a heat exchanger utilizing the heat transfer member is schematically shown in FIG 8.

(C) a conductor (conductive)

Electronic components, for example, the current integrated LSI has a structure of multiple layers. Refers to the longitudinal direction of the wiring in the LSI of the vertical layers with bi § wiring, are at present include Dohai line is used. However, due to electro Maida, single Chillon phenomenon with miniaturization, disconnection of the via is a problem. Instead of the copper wire, the vertical line, the vertically aligned single-walled force one carbon nanotube according to the present invention 'Pal click structure, or aligned single-walled carbon nanotube shape of the structure is patterned into a predetermined shape' Parc When substituted for the structure, as compared to copper flowed even current density 1 0 0 0 times, also due to the lack elect port migration phenomenon, it is possible to further miniaturization and stabilization via interconnects. One example is shown schematically in Figure 1 9.

Further, those with the conductor or wire this invention of this application the various articles to be requested conductivity, electrical products, electronic products, be utilized as a conductor or wire of optical products, and mechanical products it can.

For example, the vertically aligned single-walled force one carbon nanotube Parc structure or arrangement shape of the structure is Pas evening-learning into a predetermined shape towards single-walled carbon nanotube Parc structure according to the invention of this application high conductivity and superiority or these mechanical strength, can be refined and stabilized by the use of this product in place of the copper horizontal lines in the layer.

(D) Optical element (optical property)

Optical elements, for example, a polarizer is conventionally calcite crystals have been used, a very large and expensive optical components, also function effectively in the critical pole short wavelength region in the next generation lithography one since no, simple single-walled carbon nanotubes has been proposed as a material replacement. However, the monolayers force one carbon nanotube in the single oriented in order, and there was difficulty in such problems of creating an alignment layer structure of a macro having optical transparency. The vertical aligned single-walled force according to the invention of this application ^ carbon nanotube bulk structure or structures shaped patterned reduction are aligned single-walled and carbon Chino tube 'Parc structure to a predetermined shape, the super-oriented are shown, the thickness of the orientation film can be controlled by changing the pattern of the catalyst, it is possible strictly control thin film optical transmittance, wide from the ultrashort wave region to the infrared when used in this as the polarizer It exhibits excellent polarization characteristics in a wavelength band. Further, it is possible to very thin force one carbon nanotube alignment film to miniaturize the polarizer to function as an optical element, an example of the polarizer schematically in Figure 2 0.

The optical element of the invention of this application is not limited to polarizers, it can be applied as other optical elements by Rukoto take advantage of its optical properties.

(E) Strength reinforcing material (mechanical properties)

Conventionally, the carbon fiber reinforced material, has five 0 times stronger compared to Arumiumu, as members having a lightweight and and strength, wide aircraft parts, but that are used in sports goods such as, further weight reduction , high strength has been demanded strongly. Oriented single-walled carbon nanotube Parc structure or shape predetermined shape pattern training of has been being aligned single-walled carbon nanotube Parc structure according to the invention of this application, compared to conventional carbon-containing fiber reinforcement Te, since it has a few tens of times stronger, the use in place of these bulk structure of the conventional carbon fiber reinforced material can be obtained very high strength product. The reinforcement lightweight, in addition to a high strength, high thermal oxidation resistance (~ 3 0 0 0), flexible, there is electrically conductive, electromagnetic wave shielding property, excellent chemical resistance, corrosion resistance, fatigue 'creep characteristics are good, the abrasion resistance, the Rukoto to have a characteristic such as excellent in vibration damping, aircraft, sporting goods, including automobiles, to utilize in the field lightweight strength is required can. Figure 2 1 is aligned single-walled carbon nanotubes - a diagram showing an electron microscope (S EM) photograph of the reinforcing SWNTs fibers prepared with method of producing reinforced single-walled carbon nanotube fiber using Parc structure is there.

Incidentally, reinforcement of the present invention may also be a composite material of high strength by blending the base metal material, such as ceramics also resin.

Since supercapacitor hoards energy by the movement of charge, a large current can be passed, withstand discharge more than 1 0 million times, with features such as short charging time. Important performance as the super capacity shea evening are that the electrostatic capacitance is large, it is that the internal resistance is small. Determine capacitance is the magnitude of the pore (pores), it is known that a maximum when about 3-5 nm, called mesopores, moisture addition monolayer force one carbon synthesized by the technique It coincides with the nanotube size of. In the case of using the aligned single-walled carbon nanotube 'bulk structure, or aligned single-walled shape of the structure is patterned into a predetermined shape carbon nanotube bulk structure according to the invention of this application, all components it can be optimized in parallel. in addition, it is possible to maximize the surface area of ​​the electrode or the like, since it is possible to make internal resistance to minimize, to obtain a high performance supercapacitor can.

The vertically aligned single-walled carbon nano chew according to the invention of this application: / bulk structure, or aligned single-walled carbon carbon nanotube shape of the structure is patterned into a predetermined shape 'Parc structure the constituent materials or electrodes schematically an example of a super Canon Pasi evening that the material shown in FIG 2.

Incidentally, aligned single-walled carbon nanotube bulk structure according to the invention of this application also a material of the conventional Super Capacity shea evening not Supakyapashi evening only, an electrode material of a secondary battery such as a Lithium battery, fuel cell it can be applied as an electrode or the like air battery (negative electrode) materials.

(G) Gas storage material, absorber (P 及収 property)

Carbon nanotubes where 9 is known to exhibit a gas absorbent for hydrogen and methane, aligned single-walled carbon nanotubes according to the invention particularly large this application a specific surface area to storage 'transport of gases such as hydrogen and methane applications that can be expected to be. A conceptual diagram of a case where the aligned single-walled force one carbon nanotube Parc structure according to the invention of this application is applied as a hydrogen absorbing material 2 3 schematically shows. Also as activated carbon filters to absorb the harmful gases and substances can be substances, separation of gases, the purification. Example

The following examples will be described in more detail. Of course, there is no possibility that the invention of the following examples this application is limited.

The arrangement of the catalyst onto the substrate using a sputtering evening evaporation apparatus was performed by depositing a thickness of l nm of ferrous metals.

We investigated the relationship between the state (height) of the growth reaction time and the vertically aligned single-walled carbon nanotubes with the above conditions. The results are shown in Figure 2 4.

For comparison, but without the addition of water vapor in the same manner as described above, it was examined how the vertical Oriented single-walled carbon nanotube growth (conventional CVD method). The results after 2 minutes after the 1 5 minutes 2 5.

As a result, lose catalytic activity in a few seconds in case of growing the vertically aligned single-walled carbon nanotubes in a conventional CVD method, whereas after two minutes has stopped growing, the method of Example 1 with the addition of water vapor in, and sustained long growth as shown in FIG. 2 5, were actually observed to continue the growth of about 3 0 minutes. Also, vertically aligned single-walled force method of Example 1 - growth rate of carbon nanotube was found to be extremely fast in about 1 0 0 times those of conventional methods. Further, the vertically aligned single-walled carbon nanotubes of the method of Example 1 mixed catalyst Ya Amorubuasu force one carbon not observed, and the purity was 9 9. 9 8 mass% unpurified. On the other hand, the vertical alignment force one Pon'nanochu Bed obtained by the conventional method could not be obtained in an amount of more the purity can be measured. This result, superiority due to the water vapor addition is confirmed with respect to the growth of the vertically aligned single-walled carbon nanotubes in C VD method.

Example 2

In the following conditions, it was grown carbon nanotubes by a CVD method. Carbon compounds: ethylene; feed rate 1 0 0 sccm

The arrangement of the catalyst onto the substrate using a sputtering evening evaporation apparatus was performed by depositing a thickness of l nm of ferrous metals.

The image printed photographs with the vertically aligned single-walled carbon nanotubes grown under the conditions described above was photographed by a digital camera shown in FIG 6. In the center of about 2. 5 mm in height 〖This grown vertically aligned single-walled force one carbon nanotube of FIG. 2 6, left matchstick, right is 1 memory 1 mm at a constant parent.

2 9 and 3 0, the vertically aligned single-walled carbon nanotubes produced in Example 2 was peeled off using forceps from the substrate, the grid in ethanol electron microscope are dispersed in (T EM) placed on a shows a photographic image obtained by observing with an electron microscope (TEM). The resulting carbon nanotubes is understood to be a single layer. In addition, this catalyst and amorphous force one Bonn growth material is not contaminated with any Togawakaru. SWNTs of Example 2 was 9 9. 9 8 mass% unpurified. For comparison, the as prepared in conventional CVD method with no addition of water vapor - 3 1 a similar electron microscope of the single-walled carbon nanotubes gr own (TEM) photographic images. In Figure 3 1, black dots indicates the catalytic impurities.

The results of the vertically aligned single-walled force one carbon nanotube manufactured and thermogravimetric analysis in Example 2 shown in FIG 2. As the analyzer was Yoi ULVAC Co. Seihinoto 00-9 0 0. The portion shown in the figure A, no weight loss at low temperatures, it is understood that the amorphous carbon emissions are not present. The portion shown in the figure B, high combustion temperature of the single-walled carbon Nanochi Yubu it can be seen that a high quality (high purity). The portion shown in the figure C, and it is shown that does not contain a residue.

In addition, an impurity measurement by X-ray fluorescence for vertically aligned single-walled force one carbon nanotube prepared in Example 2. As a result, only the impurity element F e a catalyst is 0. 0 1 3ma ss% detection, other impurities were detected. Incidentally, in Example 2 in the cellulose used for immobilization vertically aligned single-walled carbon Nanochi Yubu comparable iron impurities are mixed, in Example 2 Actual of vertically aligned single-walled force one Ponna Bruno tube purity is estimated to be higher. For comparison, was subjected to impurities was measured by the same X-ray fluorescence also vertically aligned single-walled carbon nanotubes produced in the vertically aligned single-walled carbon nanotubes were produced by the conventional CVD method and the H i P CO method, conventional 17 mA ss% impurity element F e those of the CVD method, the impurity element F e those of H i PCO method was detected 3 Oma ss%.

Example 3

In the following conditions, it was grown carbon nanotubes by a CVD method.

Carbon compounds: ethylene; feed rate 75 sc cm

Atmosphere (gas): Heriumu, hydrogen mixed gas; feed rate 1000 sc cm

A pressure of 1 atmospheric pressure

Steam amount (P m): 400 ρ pm

The reaction temperature (V): 750V.

Reaction time (minutes): 10 minutes

Metal catalyst (abundance): iron thin film; 1 nm thick

Substrate: silicon wafer

The arrangement of the catalyst onto the substrate using a sputtering vapor deposition apparatus, was carried out by depositing a thickness of l nm of ferrous metals.

It was examined releasability of vertically aligned single-walled carbon nanotubes produced as described above, peeling was performed using tweezers Bok.

Figure 33 shows how the captured peeled previous vertically aligned single-walled carbon nanotube with a digital camera, FIG. 34 shows a state after peeling, Fig. 35, was placed in a container by peeling as- SWNTs purified product gr own a (3 Omg) shows. The result of this peeling test, the vertically aligned single-walled carbon Nanochi Interview part manufactured by the method of the present invention was confirmed to be very easily peeled off

Example 4

In the following conditions, it was grown vertically aligned single-walled carbon nanotubes' Pas torque structure by CVD.

Carbon compounds: ethylene; feed rate 75 sc cm

Atmosphere (gas): Heriumu, hydrogen mixed gas; feed rate l OOO sc cm

A pressure of 1 atmospheric pressure

Water vapor addition amount (P pm): 400 p pm

The reaction temperature CC): 75 Or

Reaction time (minutes): 10 minutes

Metal catalyst (abundance): iron thin film; 1 nm thick

Substrate: silicon wafer

The arrangement of the catalyst on the substrate is as follows KoTsuta.

60 seconds with an electron beam exposure resist ZEP- 52 OA in a spin Isseki one 4700 r pm, thinly adhered on the silicon wafer scratch, and 3 minutes downy one king at 200. Then, using an electron beam exposure apparatus, in the resist sticking onto the substrate to create a circular pattern with a diameter of 0.99 m at 250 tm intervals. Next, using a sputtering vapor deposition apparatus, and vapor deposition of 1 nm iron metal thickness, finally, a resist using a peeling solution ZD-MAC peeled from the substrate, a silicon wafer in which the catalyst metal is optionally patterned - the substrate was prepared.

Assembly of vertically aligned single-walled carbon nanotubes Pataengu cylindrically were obtained under the above conditions. Figure 36 shows an image obtained by shooting the shape of the aggregate by an electron microscope (SEM), in FIGS. 37 and 38, an electron microscope a state of the base of the aggregate

It shows an image taken by (SEM). Single-walled carbon nanotubes from Figure 38 it can be confirmed that oriented multiple vertically ultra high density. [Example 5]

In the following conditions, it was grown aligned single-walled carbon nanotube * Parc structure by CVD.

Figure 3 9 4 3 shows five cases of the catalyst path of evening produced by changing an training and reaction time aligned single-walled carbon nanotube bulk structure by electron microscopic (S EM) photograph. Structure of FIG. 3 9 is a thin film structure having a thickness of 5 xm, it can be seen that with flexibility. 4 0 is a view of a plurality of thin film structures from the side, it can be seen that with too flexible. 4 1 Ru multiple thin film structure der which are intricately arranged. 4 2 are different film structure thicknesses, minimum current thickness is 3 m, can be arbitrarily controlled by the patterning of the catalyst as long as the thicker. 4 3 is a structure having a complex shape. Further, FIG. 4 4 shows an image obtained by observing an example of these oriented structure from the front with an electron microscope (S EM), 4 5 an example corners of these alignment structures with an electron microscope (S EM) It shows the observed image. It can be seen that the oriented single-walled carbon nanotubes from either.

Example 7 (supercapacitors)

For characterization of the Capacity evening electrode of Example 2 obtained in aligned single-walled carbon nanotube Parc structure, aligned single-walled force one carbon nanotube Parc structure, 2.9 1 7 Fig milligrams 4 6 bonded with electrically conductive adhesive on the a 1 plate as in, it partnered the experimental cell was created for pole. As the electrolytic solution, using T EAB F 4 / PC of 1 M concentration. The constant current charge-discharge characteristics of the thus fabricated experimental cell was measured. The results are shown in FIG 4 7. From the charge-discharge curves of FIG. 4 7, vital act as that capacitor material aligned single-walled force one Bon'nanochu blanking, low internal resistance, that capacity in the high-speed charge and discharge (high current density) is not reduced substantially constant all right.

Example 8 (lithium ion battery (secondary battery))

Example 2 obtained in aligned single-walled carbon nanotube 'bulk structure, 2. was used as working electrode 4 Mi Riguramu. Counter, reference electrode was used lithium. The current collector is made of stainless steel, it formed a battery with a cell of Hohsen made commercially available. Electrolyte 1 ML i BF 4 / EC: DEC (1: 1) was used to evaluate the charge and discharge characteristics at a current density of 2 O mA / g. The results are shown in FIG. 4 8. In the first-time charge from FIG 8, very large irreversible charge was observed. Very stable a large charge is happening in potential suggest that are happening fin evening one Kahle one Chillon of lithium aligned single-walled carbon nanotube bulk structure. Second after the stable charge and discharge characteristics are obtained, the action of the battery was confirmed. It has been found that can use aligned single-walled carbon nanotube bulk structure as an electrode material for secondary batteries.

Further, tear from the same aligned single-walled force one carbon nanotube Parc structure 5 0 mg with tweezers, evenly disposed in an alumina tray, took into Matsufuru furnace. And until 5 5 0 warmed at lmin, 1 minute at 5 5 0, was heat-treated under oxygen (concentration 2 0%). Weight of the sample after the heat treatment is 4 3 mg, remaining 7 mg was burnt out. As described above, it was measured isotherms of liquid nitrogen in the same manner as above for the sample after the heat treatment (FIG. 4 9). As a result, it was the estimated specific surface area of approximately 2 0 0 0 m 2 / g . Sample after heat treatment, as compared to the sample immediately after generation, it has a large specific surface area, that the tip of the carbon nanotubes is opened suggested by heat treatment. In the drawing, P is adsorbed equilibrium pressure, P 0 is the saturation vapor pressure. as-gr unopened single-walled carbon nanotubes own (FIG. 6) is shows the high linearity at low relative pressure region of adsorption-desorption isotherms 0.5 liquid nitrogen. Against opening monolayer force one carbon nanotube of adsorption and desorption isotherms (Fig. 4 9) rises large initial adsorption, also desorption isothermal convex with large adsorption amount in 0.5 following relative pressure region attached Yotsute FEATURE: in line. It indicates adsorption-desorption isotherms of convex was opened, in the carbon nanotube, because the adsorption of the inner and outer surfaces are generated. Thus, by measuring the adsorption-desorption isotherms, Ru can identify whether force one carbon nanotube is opened or is unopened.

Example 1 0] (polarizer)

With aligned single-walled carbon nanotubes' Parc structure obtained in Example 4 was subjected to polarization dependence of the measurement of the light transmittance. Samples used having a thickness of 3 0 0 nm, measurement, helium 'neon laser one as a light source was performed using Ramudazeta 2 Fresnel rhomb wavelength plate, an objective lens, and an optical power meter scratch. Laser beam 6 3 3 nm emitted from the light source, after controlling the intensity by using an ND filter, and condensed on Oriented SWNT 'Parc structure sample surface by using an objective lens. Laser light passes through the aligned single-walled carbon nanotube 'bulk structure as the sample, condensed by using another objective lens, it led to the optical power meter scratch. Polarized light at this time the laser Ikko could be controlled in any direction by using a wavelength plate. The results are shown in FIG. 5 0.

From the results of FIG. 5 0, the use of the polarization children of this aligned single-walled carbon nanotube Parc structure was confirmed.

Moreover, to calculate the absorption yield of the sample from the transmitted light intensity at each polarized light detected by the optical power meter scratch. The results are shown in Figure 5 1. In this case, 0 degree orientation direction, 9 0 degrees is perpendicular to the orientation direction. From 5 1, the magnitude of the anisotropy of light absorption rate in the alignment direction with respect to the vertical direction of the light absorption rate in the orientation direction 1: behind that one greater than zero.

For aligned single-walled carbon nanotube bulk structure obtained in Example 2, it was measured thermal diffusivity by a laser flash method for examining the heat transfer properties. Measurement temperature room temperature, the size of the sample was 1 cm square. Measurements were carried out in three forms sample alone, it was placed a glass plate above or below the sample. It was determined thermal diffusivity from CF method Contact Yopi pulse heating energy dependency of the zero extrapolation. An example of measurement results shown in FIG 3. In FIG. 5 3, (a) a measurement data in vacuum, (b) is Isseki measurement data of the atmosphere, the horizontal axis represents time and the vertical axis represents sample temperature. Sample alone, the measurement result in a vacuum, thermal diffusivity Q is 8 0 X 1 0 -!. 5 m 2 s - 1, and was measured for some of the sample, even if changing the measurement conditions thermal diffusion rate α was 7. 0 X 1 0- 5 ~1 . 0 range of X 1 0- 5 m 2 s- 1 . As a result, good heat transfer is confirmed.

Further, in a vacuum sample temperature is heat loss effect is substantially constant small, in the atmosphere is observed decrease in sample temperature, thermal loss effect is large had appeared. For this reason, the heat dissipation effect of the aligned single-walled carbon nanotube Parc structure of this could be confirmed. Therefore, the aligned single-walled carbon nanotubes can be expected the use of the heat conductor and the heat radiating body.

Example 1 3] (conductor)

The aligned single-walled carbon nanotube Parc structure obtained in Example 2 and 1 cm X 1 cm X height 1 mm shape, at both the contacting the copper plate, cascade microphone R Tech Co. Su negation IT- 12101B- 6 Pro using one par and Ajiirento manufactured semiconductor analyzers Iza (41,550 of, and evaluate the electrical transport properties in the two-terminal method. the results are shown in FIG 4. from 5 4, current is clean with respect to the voltage it can be seen that shows the Omikku dependent (pro one bar of the amplifier reaches saturation at a current value of 0. 1 a). measurement resistance value was 6 Omega. the resistance aligned single-walled and conduction resistance through the carbon nanotube Parc structure, the contact resistance of the aligned single-walled carbon nanotube bulk structure body and the copper electrodes intended to include two, the aligned single-walled carbon nanotube bulk structure and the metal electrode small It shows that it is possible to contact with Do contact resistance. Therefore, aligned single-walled carbon nanotube Parc structure can expected to be used as the conductive material.

Claims

The scope of the claims

1. single-walled carbon nanotube purity is equal to or is 98ma ss% or more.

2. single-walled carbon nanotube according to claim 1, Toku徵 the purity of 99ma ss% or more.

3. single-walled carbon nanotube according to claim 1 or 2 purity, characterized in that at 99. 9mas s% or more.

Opening single-walled carbon nanotube according to any one of claims 1 to 3, 8. specific surface area is equal to or less than 1600 m 2 / g or more 2500 m 2 / g.

Opening single-walled carbon nanotube according to claim 7 or 8 9. specific surface area is equal to or less than 1800 m 2 / g or more 2300 m 2 / g.

10. single-walled carbon nanotube according to any one of claims 1 to 9 to Toku徵 that which was oriented.

11. SWNTs any crab of claims 1 to 10, Toku徵 that they are vertically aligned on a substrate.

12. A method for chemical vapor deposition of carbon nanotubes in the presence of a metal catalyst (CVD), the production method of carbon nano tube and Toku徵 adding an oxidizing agent to the reaction atmosphere.

Carbon nano according to claim 12, 13. oxidant and Toku徵 that the water vapor

51 corrected sheet (Tadashi则 91) Bruno method for producing a tube.

1 4. 1 0 p pm or 1 0 0 0 0 p manufacturing method of a carbon nanotube according to claim 1 3, characterized in that pm adding the following water vapor.

1 5.6 0 0 or 1 0 0 0 following claims 1 3 or 1 4 force one carbon nanotube manufacturing method according to the the addition of water vapor FEATURE: in temperature.

Carbon nanotube production method according to any one of 1 6. obtained force one carbon nanotube of claims 1 2, characterized in that a single layer 1 5 of.

1 7. method for producing carbon nanotubes according to any one of claims 1 2 to 1 6 The catalyst was disposed on the substrate and Toku徵 to grow carbon nanotubes oriented vertically to the substrate surface.

1 8. method for producing a carbon nanotube according to any one of 請 Motomeko 1 2 1 7 of a length and wherein the obtaining one or more carbon nanotubes.

1 9. manufacturing method of a carbon nanotube according to any one of claims 1 2 to 1 8, Toku徵 that obtain the following carbon nanotube 1 0 m or more 1 0 cm in length.

After growing the 2 0. carbon nanotubes, solutions and method of manufacturing the carbon nanotube according to any one of claims 1 2 to 1 9, Toku徵 that can be separated from the catalyst or the substrate without solvent exposed.

2 1. Method of manufacturing the carbon nanotube according to any one of claims 1 2 to 2 0 to that purity obtained carbon nanotube is 9 8 mass% or more and FEATURE:.

2 2. production method of a carbon nanotube according to any one of claims 1 2 to 2 1 purity to FEATURE: obtaining a carbon nanotube is 9 9 mass% or more.

2 3. Method of manufacturing the carbon nanotube according to any one of claims 1 2 2 2 of purity, characterized in that to obtain a carbon nanotube is 9 9. 9 mass% or more.

Method for producing a carbon nanotube according to any one of claims 12 to 23, Toku徵 to obtain a 52 correction expired was ¾ paper one carbon nanotube.

25. specific surface area of 800 m 2 / g or more 1200 m 2 / g or less unopened monolayer force - method of manufacturing the carbon nanotube according to claims 12 to one of 24 to Toku徵to obtain a carbon nanotube.

Method for producing a carbon nanotube according to any one of claims 12 to 23, 26. specific surface area, characterized in that to obtain the opening monolayer force one carbon nanotube is not more than 1600 m 2 / g or more 2500 m 2 Zg.

27. specific surface area of 1800 m 2 / g or more 2300 m 2 / g or less is opening monolayer force - method of manufacturing the carbon nanotube of any crab of claims 12 to 23, 26 to Toku徵to obtain a carbon nanotube.

28. a plurality of aligned single-walled force one carbon nanotube, aligned single-walled carbon nanotube bulk structure according to Toku徵 the height is more than 10 m.

29. aligned single-walled carbon nanotube bulk structure according to claim 28 in which the height is characterized in that or more and 10 cm or less 1 O m.

Aligned single-walled carbon nanotube bulk structure according to claim 28 or 9, characterized in that 30. purity of 98mas s% or more.

Aligned single-walled carbon nanotube Parc structure according to any one of 30 claims 28 to Toku徵 that 31. purity of 99ma ss% or more.

Claims 28 to Toku徵 that 32. purity of 99. 8mas s% or more

Aligned single-walled carbon nanotube Parc structure according to any one of 31.

It claims 28 to Toku徵that 33. specific surface area of 600 meters 2 Zg more

Aligned single-walled carbon nanotube Parc structure according to any one of 32.

4 0. orientation and optical properties in a direction perpendicular thereto, the electrical properties, claims, characterized that you anisotropic at least one of the mechanical properties, magnetic properties and thermal anisotropy aligned single-walled carbon nanotube Parc structure according to any one of 2 8 3 9.

. 4 1 size of the alignment direction and the direction perpendicular anisotropy thereto, 1 to the value of the lesser value larger: as claimed in claim 4 0 to Toku徵 that is three or more aligned single-walled carbon nanotube bulk structure.

4 2.1 for values ​​towards the size of the alignment direction perpendicular to the direction of anisotropy in it, not small, the larger value: Claim 4 0 or 4 1, characterized in that 5 or more aligned single-walled carbon nanotube bulk structure of the mounting come to.

4 3. The size of the alignment direction perpendicular to the direction of anisotropy in it, for the value of the lesser value larger 1: 1 4 of claims 4 to 0, characterized in that 0 or more single-walled carbon nanotube bulk structure according to 2 Neu or misalignment.

4 4. aligned single-walled carbon nanotubes Parc structure according to claim 2 8, FEATURE: 4 3 of that is obtained can be obtained without being exposed to the solvent contact Yopi solvent .

4 8. metal catalyst is patterned on a substrate, a plurality of single-walled carbon nanotubes by chemical vapor deposition (CVD) Parc structure to orient in a predetermined direction against the substrate surface in the presence of the metal catalyst a method for the manufacturing method of the aligned single-walled carbon nanotube bulk structure characterized by adding an oxidizing agent to the reaction atmosphere.

5 4. shape a metal catalyst bulk structure patterned and Chikaraichi Bon'nanochu - the aligned single-walled carbon nanotube bulk structure according to any one of claims 48 to 53, Toku徵 to control the growth of flops Production method. .

55. After the bulk structure was grown, the solution and the aligned single-walled carbon nanotubes according to claims 48 to 54 or Re noise not exposed to solvent catalyst or, characterized in that it can be separated from the substrate method of manufacturing a bulk structure.

Method for producing aligned single-walled carbon nanotube bulk structure according to any one of claims 48 to 55 56. purity; and obtaining Parc structure is 98ma ss% or more.

Method for producing aligned single-walled carbon nanotube Parc structure according to any one of claims 48 to 56 57. purity and Toku徵 obtaining a bulk structure at 99ma ss% or more.

58. purity 99. 9 mA ss% or more at which aligned single-walled carbon nanotubes according to any of claims 48 57, characterized in that obtaining a bulk structure - method of manufacturing bulk structure.

Method for producing aligned single-walled carbon nanotubes * Pas torque structure according to any one of claims 48 to 58 59. specific surface area and Toku徵to obtain the Parc structure is 600 meters 2 / g or more.

Method for producing aligned single-walled carbon carbon nanotube Parc structure according to any one of claims 48 to 59 60. specific surface area and wherein the obtaining Parc structure is less than 800 m 2 Zg least 250 Om ^ g .

61. specific surface area of 1000 m 2 Zg to obtain a more 200 Om 2 / g or less is Parc structure of claims 48 to Toku徵60 of one of aligned single-walled force one carbon nanotube bulk structure according to Production method.

62. specific surface area of 600 meters 2 Zg least 1300 m 2 / g or less unopened monolayer force - aligned single layer according to any one of obtaining a bulk structure made of carbon nanotubes of claims 48 to Toku徵58 manufacturing method of a carbon nanotube bulk structure.

6 8. The size of the alignment direction anisotropy in a direction perpendicular to it, one for the value of the direction value is less the larger: claims, characterized in that to obtain a 5 or more at a bulk structure

Claims, characterized in that to obtain a 1 0 or in which Parc structure: 6 9. size of the alignment direction and the anisotropy in the direction perpendicular thereto, the larger value is 1 for values ​​of the lesser method for producing aligned single-walled carbon nanotube Parc structure according to any one of claim 6 7 6 8.

7 1. Single-walled carbon nanotube according to any one of claims 1 1 1, or the aligned single-walled carbon nanotubes' Pal click structure according to claim 2 8 4 7, substrate and catalyst and at least an apparatus for separating from one of the separation device according to Toku徵 further comprising cutting means or suction means.

7 2. method of manufacturing the carbon nanotube to Toku徵 that combines the step of Yabu壌 subsidiary product to deactivate the process and catalyst for growing carbon nanotubes.

7 3. Carbon nanotube manufacturing method of claim 7 wherein the carbon nano-tubes, characterized in that each step is carried out under a gas phase or under a liquid phase.

7 5. claims 1 to 1 1 of single-walled carbon nano Ju part according to any one, or aligned single-walled carbon nanotubes according to any of claims 2 8 4 7. Use the bulk structure heat radiator to Toku徵 the be had.

9 0. claimed single-walled carbon nanotubes as set forth in claim 1 in any one 1, or aligned single-walled force one carbon nanotube according to any of claims 2 8 4 7, using bulk structure optical element according to Toku徵 that.

9 1. The optical element according to claim 9 0, wherein the optical element is a polarizer.

9 2. Double if the material to Toku徵 by containing an optical device according to claim 9 0 or 9 1.

9 3. Optical articles and Toku徵 further comprising an optical element according to claim 9 0 or 9 1.

9 4. single-walled carbon nanotube according to claim 1 1 1, or using the aligned single-walled force one carbon nanotube 'bulk structure according to any one of claims 2 8 4 7 reinforcing material, characterized in that.

9 5. reinforcement according to the monolayers force one carbon nanotube or aligned single-walled force one carbon nanotube Pal click structure was a laminate to claim 9 4, Toku徵.

Composite material to Toku徵 that it contains reinforcing material according to 9 6. 9. 4 or 9 5.

9 7. Metal, composite material according to claim 9 6 at least one selected from ceramics and resin, characterized in substrate and to Rukoto.

Battery, characterized in that the electrode material according to the electrode 1 0 0. 9. 8.

1 0 1. battery is at least selected from secondary battery, fuel cells and air cells - cell according to claim 1 0 0 to Toku徵 to be species.

1 0 2. Claim single-walled carbon nanotube according to any one of 1 to 1, or the electrode material aligned single-walled carbon nanotubes' Pas torque structure according to claim 2 8 4 7 or capacitor or supercapacitor, characterized in that the constituent material.

PCT/JP2005/0142392004-07-272005-07-27Single-layer carbon nanotube and alinged single-layer carbon nanotube bulk structure, and their production process, production apparatus and use
WO2006011655A1
(en)